The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes: a physical picture
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We describe the vibrational transitions of the donor unit in water dimer with an approach that is based on a three-dimensional local mode model. We perform a perturbative treatment of the intermolecular vibrational modes to improve the transition wavenumber of the hydrogen bonded OH-stretching transition. The model accurately predicts the transition wavenumbers of the vibrations in water dimer compared to experimental values and provides a physical picture that explains the redshift of the hydrogen bonded OH-oscillator. We find that it is unnecessary to include all six intermolecular modes in the vibrational model and that their effect can, to a good approximation, be computed using a potential energy surface calculated at a lower level electronic structure method than that used for the unperturbed model.
Originalsprog | Engelsk |
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Artikelnummer | 184309 |
Tidsskrift | Journal of Chemical Physics |
Vol/bind | 140 |
Antal sider | 9 |
ISSN | 0021-9606 |
DOI | |
Status | Udgivet - 2014 |
ID: 131023733